Disazo dyestuffs



United States Patent DISAZO DYESTUFF S Herbert-Joachim Exner,Koln-Stammheim, Germany, as-

signor to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany,a corporation of Germany No. Drawing. Application March 7, 1957 SerialNo. 644,464

Claims priority, application Germany May 19, 1956 7 Claims. (Cl.260-160) The present invention relates to disazo dyestufis and to aprocess for their manufacture; more particularly it relates to disazodyestuffs of the following formula HzN N H:

wherein A, X and Y have the meaning as previously defined, with 1 mol ofa l-aryl-3-methyl-5-aminopyraz0le and with 1 mol of the same azocomponent or 1 mol of an aminonaphthalene.

The tetrazo components may be prepared by reaction ofnitrobenzene-sulfochlorides of the general formula with aromaticdihydroxy compounds of the general fiormula wherein A, X and Y have theabove-mentioned significance, in an aqueous medium in the presence ofacid-binding agents or in suitable organic solvents and subsequentreduction of the nitro group according to known processes. It is notabsolutely essential that 1 mol of the aromatic dihydroxy compound isreacted with 2 mols of the same nitrobenzene-sulfochloride. It is alsopossible to react consecutively 1 mol of a nitrobenzene-sulfochlorideand another mol of a diflerent nitrobenzene-sulfochloride, or even 2mols of a mixture of different nitrobenzene-sulfochlorides, with thedihydroxy-oompound. The conversion of the dinitro compounds into thecorresponding diamino compounds is effected by known processes.

. Suitable tetrazo components according to the definition of theinvention are, for example: 1,2-dihydroxybenzenebis (2 aminophenyl 1sulfonic acid) ester, 1,2 di- 2,862,919 Patented Dec. 2, 1958hydroxybenzene bis (3 aminophenyl 1 sulfonic acid) ester,1,2-dihydroxybenzene-bis-(4 aminophenyll sulfonic acid) ester, 4,4dihydroxydiphenyl bis (2 aminophenyl 1 sulfionic acid) ester, 4,4 dihydroxydiphenyl bis (3 aminophenyl l sulfonic acid)- ester, 4,4dihydroxydiphenyl bis (4 aminophenyl l sulfonic acid) ester, 1,5dihydroxynaphthalene bis (2 aminophenyl 1 sulfonic acid) ester, 1,5dihydroxynaphthalene bis (3 aminophenyl 1 sul fonic acid) ester, 1,5dihydroxynaphthalene bis (4 aminophenyl l sulfonic acid) ester, di (phydroxy phenyl) dimethylmethane bis (2 aminophenyl 1 sulfionic acid)ester, di (p hydroxyphenyl) dimethyl methane bis (3 aminophenyl 1sulfonic acid) ester, di (p hydroxyphenyl) dimethylmethane bis (3 amino6 chlorophenyl 1 sulfonic acid) ester, di (p hydroxyphenyl)dimethylmethane bis (4 aminophenyl l sulfonic acid) ester, 1,3 dihydroxybenzene bis (3 amino 4 chlorophenyl l sulfonic acid) ester, 1,3dihydroxybenzene bis 4 chlorophenyl l sulfonic acid) ester.

Further diamines may be obtained, for example, by reduction of thereaction products from 1 mol of di-(phydroxyphenyl')-dimethylmethane and1 mol of 2-nitrobenzene-sulfochloride and 1 mol ofB-nitnobenzene-sulfochloride. Instead of 1 mol ofdi-(p-hydroxyphenyl)-dimethylmethane there may also be useddi-(p-hydroxyphenyl) -methylmethane, di- (p-hydroxyphenyl -methane,4,4-dihydroxy-diphenylsulfone or 1,3-dihydroxybenzene.

According to the definition there is employed as coupling agent at least1 mol of a 1-aryl-3-methyl-5-aminopyrazole per mol of the tetrazocompound. The aryl radical may contain non-ionic or ionic substitutents,such as sulfonic acid or carboxylic acid groups. The following compoundsmay be mentioned as examples: 1 phenyl 3 methyl 5 aminopyrazole, 1 (2'sulfophenyl) 3 methyl 5 aminopyrazole, l (3' sulfophenyl) 3 methyl 5aminopyrazole, 1 (4 sulfophenyl) 3 methyl 5 aminopyrazole, 1 (3'carboxyphenyl) 3 methyl 5 aminopyrazole, l (2' chloro 5' sulfo phenyl) 3methyl 5 .aminopyrazol'e, 1 (2,5' di chloro 4' sulfophenyl) 3 methyl 5aminopyrazole, l (6 sulfonaphthyl 2 3 methyl 5 aminopyra zole, l (8sulfonaphthyl 2) 3 methyl 5 amino pyrazole, l (4, 8' disulfonaphthyl 2')3 -methyl 5 aminopyrazole.

For the further coupling, the following compounds may be used:

1 aminonaphthalene, l amino 8 chloronaphtha lene, l amino naphthalene2-,3-,4-,5-,6-,7- or 8- sulfonic acid, 1 aminonaphthalene 2,5 disulfonicacid, 1 aminonaphthalene 3,6 disulfonic acid, 1 amino naphthalene 3,7disulfonic acid, 1 aminonaphthalene 3,8 disulfonic acid, 1aminonaphthalene 4,6 disul fonic acid, 1 aminonaphthalene 4,7 disulfonicacid, 1 aminonaphthalene 4,8 disulfonic acid, 1 amino naphthalene 5,7disulfonic acid, 1 aminonaphthalene 2,5,7 trisulfonic acid, 1aminonaphthalene 3,5,7 tri sulfonic acid, 1 aminonaphthalene 3,6,8trisulfonic acid, 1 aminonaphthalene 4,6,8 trisulfonic acid, 2aminonaphthalene 2 aminonaphthalene 5-,6-,7- or 8- sulfonic acid, 2aminonaphthalene 3,6 disulfonic acid,

2 aminonaphthalene 3,7 disulfonic acid, 2 amino naphthalene 4,7disulfonic acid, 2 aminonaphthalene 4,8 disulfonic .acid, 2aminonaphthalene 5,7 disul fonic acid, 2 aminonaphthalene 3,6,8trisulfonic acid,

2 aminonaphthalene 4,6,8 trisulfonic acid, 2 amino (2 aminoponents permol' of tetrazo compound, it is possible to prepare symmetrical orasymmetrical disazo dyestuffs.

The new disazo dyestuifs dye animal fibres such as wool and silk andsynthetic fibres such as polyamide and polyurethane fibrefs in clearshades from a 'weakly acid or neutral bath. The dyeing possesses verygood fastness properties to light and Wetting, and the dyestufis aredistinguished by a good levelling power.

The following examples are given for the purpose of illustrating 'theinvention, Without, however, limiting it thereto:

Example 1 56.0 grams of 4,4-dihydroxy-diphenylsulfone-bis-(2-amino-phenyl-sulfonic acid)-ester are tetrazotized with 13.8 grams ofsodium nitrite To the tetrazo solution there are added 50.4 grams ofl-(3-sulfophenyl)- 3-rnethyl-5-aminopyrazo1e, the solution isneutralized with sodium acetate and coupling completed while cooling.The isolated dyestufi corresponds in the free acid state to the formula:

completed. The isolated dyestuff which corresponds in the free -acidstate to'the'formula:

dyes wool in yellow shades of very good fastness to light and wetting. 7

Example 4 54.0 grams of di-(p-hydroxyphenyl)-dimethylmethane- It dyeswool in yellow shades of very good fastness to light and wetting.

Example 2 42.0 grams ofl,2-dihydroxybenzene-bis-(2-aminophenyl-l-sulfonic acid)-ester aretetrazotized with 13.8 grams of sodium nitrite, the tetrazo solution istreated with 61 grams of l-(8-sulfonaphthyl-2')-3-methyl-5-aminopyrazoleand coupled with addition of sodium acetate.

I SOaH The isolated dyestufi corresponds in the free acid state to theformula:

1t dyes wool in yellow shades fast to light and wetting. Example 3 42.0grams of 1,3 dihydroxybenzene bis (Z-aminophenyl-l-sulfonie acid)-esterare tetrazotized with 13.8

grams of sodium nitrite, and the solution is treated with 6i grams ofl-(6-sulfonaphthyl-2)-3-methyl-5-aminopyrazole. After neutralizing thesolution, coupling is bis-(2-aminophenyl-l-sulfonic acid)-ester aretetrazotized with 13.8 grams of sodium nitrite. A freshly precipitatedsuspension of 23.9 grams of 2-amino-8-hydroxynapthalene-6-sulfonic acidis slowly run into the tetrazo solution and stirring is continued withcooling until the tetrazo reaction has ceased. 25.2 grams ofl-'(3-sulfo'phenyl)- 3-methyl- 5-aminopyrazole are then added and thefinal coupling is completed by heating. The dyestufi corresponds in thefree acid state to the formula:

and dyes wool in yellowish red shades of very good fastness to light andwetting.

Example 5 54.0 grams of di-(p-hydroxyph'enyl)-dimethylrmethanebis-(3-aminophenyl-1-sulfonic acid) -ester are tetrazotized with 13.8 gramsof sodium nitrite, and 50.4 grams of 1-(3 sulfophenyl)-3-methyl-5-aminopyrazole are added. After neutralizing the-mixturecoupling-is completed; The

isolated dyestufi corresponds in the free acid state to the formula a Itdyes wool in yellow shades of very good fastness to light and wetting;

Example"? 42.0 grams of1,2-dihydroxybenzene-bis-(3-aminophenyl-l-sulfonic acid)-ester aretetrazotized with 13.8 grams of sodium nitrite. ,A suspension of 23.9grams of 2-amino-8-hydr oxynaphthalene-6 sulfonic acid is slowly runinto the tetrazo solution, and coupling is carried out until the tetrazoreaction disappears. 30.5 grams oflv(6'-sulfonaphthyl-2)-3-methyl-5-aminopyrazole are then added andcoupling is completed by heating. The

isolated dyestutf which corresponds in the free acid state to theformula:

. Q lfiHg OSOA) 0.02SQ

7, 0 H dyes wool inye'llowish red shades of good fastness to light andwetting.

Example 8 dyes wool in yellow shadesofwery godd'fa'stnessto light andwetting. :11;. I

SOgH

V Example '9' f I-'. 54.0 grams of the product which is obtained byr.educ-' tion of a compound obtained by reaction of 22.8 grams ofdi-(p-hydroxyphenyl) -dimethylrnethane with 22.1 grams of2-nitrobenzene-sulfochloride and 22.1 grams of3-nitrobenzene-sulfochloride are tetrazotized with 13.8 grams of sodiumnitrite and the clear tetrazo solution is treated with 50.4 grams of1-(3-sulfophenyl)-3-methyl-5-aminopyrazole; Coupling is completed by theaddition of acidbinding agents. The isolated dyestuif corresponds in thefree acid state to the formula SOSH It dyes wool inyellow shades of verygood fastness to light and wetting.

Example 10 2 grams'of the dyestufi described in Example 1 are dissolvedin 3 litres of water. After the addition of 10 grams of crystallizedsodium sulfate and 2 millilitres of 30 percent acetic acid, 10 grams ofa woolen-fabric. are. introduced in the dye. bath, thebath heated tovboiling: temperature within 40' minutes and boiled for 30 minutes. Afterthe addition of 2 millilitres of formic acid the bath is heated for afurther 30 minutes and the dyed fabric is rinsed with water and dried. Ayellow shade is thus obtained.

Example 11 I 54.0 grams ofdi-(p-hydroxyphenyl)-dimethylmethanebis-(2-aminophnyl-l-sulfonicacid)-ester are tetrazotized with 13.8 grams of sodium nitrite. Afreshly precipitated suspension of 30.5 grams of 1-(8'-sulfonaphthyl2f)-3- methyl-5-aminopyrazol is' added, the mixture diluted with Waterand neutralized with sodium acetate. 22.4 grams of2-amino-naphthalene-6-sulfonic acid are then added and the finalcoupling is completed by heating. The isolated dyestulf whichcerrespondsin the free acidstate to the formula:

dyes wool in reddish-yellow shades of very good fastness to light andwetting.

I claim:

1. A disazo dyestuff corresponding to the general forv mula wherein Rmeans a radical selected from the group con- 30 sisting of1-sulfophenyl-3-methyl-5-aminopyrazole and 1-sulfonaphthyl-3-methyl-5-aminopyrazole, R stands for a radical selectedfrom the group consisting of l-sulfophenyl-3-methyl-5-aminopyrazole,1-sulfonaphthyl-3-methyl-5- coupled in o-position to the amino group,and A stands for a divalvent radical selected from the group consistingof members of the phenylene, diphenylene, diphenylenesulfone, and thedimethyl-diphenylene-methane series.

2. A disazo dyestufi corresponding to the formula 25 wherein R is1-sulfophenyl-3-methyl-5-aminopyrazolyl aminopyrazole,Z-aminonaphthalene-sulfonic acid and 2-. aminonaphthol-sulfonic acid,the pyrazolyl radicalsbeing (mil coupled in the 4-position andthe-naphthyl radicals being CH; E

6. The disazo dyestufl corresponding to the formula omeQ Hos

7. The disazo dyestuif corresponding to the formula No references cited.

1. A DISAZO DYESTUFF CORRESPONDING TO THE GENERAL FORMULA